CN1896286B - Method for producing direct iron-reduction by iron-ore briquet self-production reproduced gas - Google Patents
Method for producing direct iron-reduction by iron-ore briquet self-production reproduced gas Download PDFInfo
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- CN1896286B CN1896286B CN2006100128373A CN200610012837A CN1896286B CN 1896286 B CN1896286 B CN 1896286B CN 2006100128373 A CN2006100128373 A CN 2006100128373A CN 200610012837 A CN200610012837 A CN 200610012837A CN 1896286 B CN1896286 B CN 1896286B
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Abstract
The present invention relates to a method of producing direct reduction iron with self-produced reduction gas of iron ore-coal pellet. With the coal in the iron ore-coal pellet as the whole reducing agent, the gas generated by self-pyrolysis of the coal in the iron ore-coal pellet as the self-produced reduction gas and the low heat value gas as the fuel heating the reduction gas, the self-produced reduction gas is recycled and reduces the iron ore into direct reduction iron in reducing atmosphere at high temperature. The present invention replaces the external reduction gas with the self-produced reduction gas facilitating zero release of greenhouse gases in the production of direct reduction iron and the realization of clean production.
Description
Technical field
The present invention relates to the direct reduction smelting method of iron ore briquet, particularly relate to a kind of method of utilizing the self-produced reducing gas of iron ore briquet to produce direct-reduced iron.
Background technology
The production method of direct-reduced iron mainly is divided into gas base method and coal-based method, gas base method has worldwide obtained using widely, be mature technology, but this method make the area of Sweet natural gas shortage use this technology to be restricted owing to adopt Sweet natural gas as reducing gas and thermal source.For the area of rich coal resources, use coal-based method to produce direct-reduced iron and have realistic meaning.Coal-based method is produced direct-reduced iron and is mainly contained methods such as revolution cellar for storing things, cellar for storing things, flint road, pot furnace, rotary hearth furnace, shaft furnace, these methods all are to adopt in coal gas or the stove self produced gas as reducing gas, heated oxide iron ball nodulizing or contain charcoal iron ball nodulizing and produce direct-reduced iron.
BL direct-reduced iron production technique is developed jointly by Shanghai Baoshan Iron and Steel Company and southern Shandong fertilizer plant, be that employing iron oxide pellet nodulizing and lump ore are raw material, raw material is oxidized to acid pellet through shaft furnace earlier, feeds the reducing gas of producing by mill coal again, utilize acid pellet to produce direct-reduced iron.This technology is called two-stage method, and production technique is long, the energy consumption height, and investment is big, the cost height.
The production method (ZL 98119030) that the coal-based direct reduction method is produced direct-reduced iron has been finished in the development of the metallurgical designing institute in Beijing, its method is that cold bonded iron pellet, the special-purpose moulded coal that will prepare respectively mix by a certain percentage with fritter bituminous coal and Wingdale, add in the reduction shaft furnace, produce coal gas through outer heating and internal heating, the cold bonded iron pellet is directly reduced, surplus gas is used for outer heating, and direct-reduced iron separates through the screening magnetic separation with cinder.Above-mentioned processing method needs to add in addition moulded coal and Wingdale when producing direct-reduced iron, contain cinder and reduced iron in the product, needs separating treatment, and the moulded coal of adding and fritter bituminous coal can only be produced semicoke, can not produce formed coke, and utility value is lower.
In " single stage method is produced the processing method and the production unit of direct-reduced iron " (ZL 02160316) patent, providing a kind of is raw material with carbon containing cold consolidation iron ball nodulizing, producer gas and coke-oven gas are done reducing gas, the method that adopts indirect heating and direct heating to combine with indirect heating makes carbon containing cold consolidation iron ball nodulizing direct reductive direct-reduced iron production method under 900～1300 ℃ of temperature.
The production method of above the sort of direct-reduced iron no matter, reducing gass such as the coke-oven gas that all needs to provide a large amount of in process of production, producer gas, Sweet natural gas produce a large amount of reduction tail gas simultaneously.At present the main purposes of the reduction tail gas that produces is that the heating flame chamber that acts as a fuel passes to the reduction chamber with heat through furnace wall after drawing from reduction reactor or reduction reaction district; Perhaps be used for adding the checker brick or the refractory ball of thermal heat storing type reducing gas process furnace, heat accumulating type reducing gas process furnace will be sent in the reduction shaft furnace after the reducing gas heating again, thermal energy transfer is given contain charcoal iron ball nodulizing; Perhaps being used for industry cellar for storing things stoves such as burning heating coke oven, hotblast stove, gas-fired furnace uses.
In fact; with carbon containing cold consolidation iron ball nodulizing is raw material; when producer gas and coke-oven gas are done reducing gas production direct-reduced iron; reducing gas has three functions: heat transfer effect, maintenance reducing atmosphere effect and reduced iron effect; what wherein play a major role is the effect that heat transfer effect and maintenance reducing atmosphere, protection reduction process are normally carried out, and promptly dilutes the CO that reduction process produces
2And H
2O and the carbon containing cold consolidation iron ball nodulizing in stove transmit the effect of heat.Join charcoal in the carbon containing cold consolidation iron ball nodulizing of an actual main reductive action, i.e. charcoal in coal dust in the carbon containing cold consolidation iron ball nodulizing, coke powder, the binding agent.Only at the interior charcoal of joining when being lower than the required C of reduction reaction, CO in the reducing gas and H
2Just can play main reductive action as reductive agent.Therefore, produce in the reduction tail gas that direct-reduced iron produces except containing CO
2And H
2Outside the O, main still by CO, H
2, CH
4Be grouped into Deng being reduced into, have very strong reducing property,, and adopt producer gas and coke-oven gas in addition again, can cause the unreasonable use of the energy and waste greatly as reducing gas if only it is acted as a fuel use.
Summary of the invention
The pyrolysis gas that the objective of the invention is to utilize the coal pyrolyzing in the iron ore briquet to produce all replaces the outside reducing gas that provides to produce direct-reduced iron, with reasonable energy utilization, saves the energy.
The present invention finds that the iron ore briquet after the heating has exothermic phenomenon in the pyrolytic process of coal, can make full use of the heat that heat release produces, and is used for the further heating and the pyrolysis of iron ore briquet coal, is used for the direct reduction to iron ore.Therefore, the present invention all with the coal in the iron ore briquet as reductive agent, the gas that produces with coal pyrolyzing in the iron ore briquet is as reducing gas, under the atmosphere of high temperature reduction gas with reduction of iron ore, to produce direct-reduced iron.
The concrete grammar that the present invention produces direct-reduced iron is:
Before blow-on, the gas mixture of one or more in preparation nitrogen, coke(oven)gas, gas maked coal, Sweet natural gas, the coal-seam gas is as starting source of the gas earlier.
To start source of the gas earlier and be full of reduction shaft furnace and displace furnace air, will be heated to pyritous again and start source of the gas and feed in the reduction shaft furnace, heating iron ore briquet makes in the pelletizing part of coal pyrolysis produce and contains H
2, CO and CH
4Pyrolysis gas, part of coal is as the reductive agent reducing iron ore, produces to contain CO
2And H
2The reduction tail gas of O;
The pyrolysis gas that produces is discharged by furnace roof with reduction tail gas, through desulfurization, take off CO
2After the purifying treatment, become self-produced reducing gas;
Self-produced reducing gas with heating progressively substitutes high startup temperature source of the gas, feeds in the reduction shaft furnace until replacing high startup temperature source of the gas fully, continues heating iron ore briquet, produces new pyrolysis gas and reduction tail gas, by the furnace roof discharge, through desulfurization, take off CO
2After the purifying treatment, become self-produced reducing gas, form the cyclic production and the use of self-produced reducing gas, simultaneously, self-produced reducing gas is also participated in the reduction reaction of iron ore in the part iron ore briquet directly, and produces reduction tail gas;
Circulation so repeatedly, the continuous production of realization direct-reduced iron.
According to general theory, the direct reduction of iron ore briquet is a strong endothermic reaction, and the coal carbonization pyrolysis also is thermo-negative reaction, if the heat of direct-reduced iron only is provided with the heat of self-produced reducing gas, is difficult to realize heat balance in the reduction shaft furnace.But the present invention has found in test the exothermic phenomenon of pyrolysis of coal, makes the heat balance problem in the direct reduction shaft furnace obtain solution.Concrete reason is: for the lower coal of metamorphic grade, because existing many oxygen palaces that contain in the coal can roll into a ball, as carboxyl, hydroxyl, carbonyl, quinonyl, ether and heterocycle (as furans) etc., wherein carboxyl is least stable, if coal is heated to more than 200 ℃, tangible decarboxylic reaction and coal deoxygenation can take place, and generate CO and CO
2And emit heat.Coal in the iron ore briquet contains a large amount of CO, H in the gas of generation in retort process
2, CH
4, C
mH
nAnd tar class material, be enclosed in the pelletizing and can not in time discharge, make and produce gaseous tension in the pelletizing.Owing to adopt the lower coal of metamorphic grade to do main coal blending, owing to contain a large amount of H in the dry distillation gas
2, because Fe is arranged
3O
4, FeS, Fe
2O
3Make catalyzer, owing to have tar class material and binding agent to make solvent, owing to have the continuous heat supply of high-temperature gas and temperature to reach coal hydrogenation pyrolytic temperature, because certain recovery time is arranged, because at the inner gaseous tension that produces of pelletizing, possessed coal hydrogenation liquefaction, gasification, whole primary conditions of dry distillation gas and coal copyrolysis.
Wherein, during in furnace temperature＜618 ℃, H
2Also prime mover than CO is little, therefore, during in furnace temperature＜618 ℃, mainly is the thermopositive reaction of coal hydrogenation pyrolytic, has produced coal hydrogenation gasification C+2H
2=CH
4The thermopositive reaction of+77.8KJ has produced coal hydrogenation liquefaction heat release and has reached 46～54KJ/molH
2Strong exothermal reaction.Liberated heat can be directly used in pyrolysis of coal, raising pelletizing temperature and the directly reduction of iron ore briquet.The fluent meterial that produces plays interior cohesive action, and to keep pellet strength, the gas of generation mainly is and the similar raw gas of coking.
When furnace temperature is in 618～900 ℃, H
2Also prime mover than CO is big, this moment H
2Can reduced iron, also can generate CH with the hydrocarbon reaction in coal and the coal
4In hydrocarbon polymer.H
2The reaction of reduced iron is thermo-negative reaction, and H
2With the building-up reactions of coal be strong exothermal reaction.In the pyrolysis of coal stage in temperature＜900 ℃, iron ore briquet inside is the gas, liquid, solid three-phase, and wherein fluent meterial plays interior cohesive action, and raises with furnace temperature, fast to gaseous state and solid-state conversion, produces polycondensation for the first time, forms the induration form of semicoke and iron ore.Mainly contain H in the reduction tail gas that produces
2O, CO
2, CO, CH
4, H
2, H
2Compositions such as S.
When furnace temperature is higher than 900 ℃, mainly be coal and iron, H
2Direct reduction reactor with iron.At reduction phase, temperature＞900 ℃, semicoke continues to discharge and contains H
2Volatile matter, H wherein
2Generate Fe and H with the iron ore reaction
2O; Generate Fe and H with sulfide
2S produces desulphurization reaction; Enter the self-produced reducing gas of high temperature of reduction shaft furnace and the direct reduction reactor of iron ore reaction and iron ore briquet self and generate Fe and CO, CO
2, H
2O etc. reduce tail gas; The induration of the fixed conversion coking of semicoke and iron ore and iron ore and iron ore reduction thing.Along with proceeding of reduction reaction, quicken to consume charcoal, charcoal among Jiao and iron ore reaction generate Fe, CO and CO
2Self-produced reducing gas and iron ore reaction generate Fe, CO, CO
2And H
2O; Produce fe and crystal stock progressively, and produce polycondensation for the second time, finished the whole process that is reduced to direct-reduced iron at solid-state iron ore briquet down.
Contain a large amount of CH in coal pyrolysis gas of discharging by furnace roof and the reduction tail gas
4, do not have the CO, the H that have reacted
2And hydrocarbon gas, and dust, sulfide, H
2O, CO
2With tar class material.Above-mentioned gas is removed tar, dust through cooling, desulfurization, removes H
2O, remove CO
2After the purification, can directly use without cracking as self-produced reducing gas.Self-produced reducing gas can utilize the interior iron ore of stove as catalyzer after entering reduction shaft furnace, utilizes the oxygen in the iron ore, the H that pyrolysis of coal produces
2The H that O and reduced iron produce
2O realizes the reformation certainly of reducing gas, makes CH
4Cracking produces H
2And CO.
In original production also, also need or send into shaft furnace before self-produced reducing gas is sent into shaft furnace sometimes after, in stove, provide oxygen, to improve and to adjust the control furnace temperature.
One of method of oxygen supply gas is that oxygen and the burning of self-produced reducing gas are produced high-temperature gas, high-temperature gas is blended in the self-produced reducing gas again.Concrete grammar is to adopt the Continuous Heat Transfer mode that self-produced reducing gas is heated to 600 ℃, self-produced reducing gas and oxygen mix burning with 600 ℃ of parts, make its burning gas temperature reach 1400～1600 ℃, then burning gas is blended in 600 ℃ the self-produced reducing gas,, send in the reduction shaft furnace when temperature reaches 900～1300 ℃ as self-produced reducing gas with mixed gas.
Two of the method for oxygen supply gas is to adopt the needle-like oxygen supply directly to provide oxygen in self-produced reducing gas, and with oxygen-supplying amount be controlled at fire a little below.Specifically be before self-produced reducing gas feeds reduction shaft furnace, according to self-produced reducing gas: oxygen=10～100: 1 volume ratio is mixed oxygen in self-produced reducing gas, on the one hand, oxygen and the burning of self-produced reducing gas produce heat heats up self-produced reducing gas, in order to improve and adjustment control furnace temperature; On the other hand, the CH in oxygen and the self-produced reducing gas
4The reaction of generation Pintsch process produces H
2And CO, to realize the reformation certainly of self-produced reducing gas.
Startup source of the gas of the present invention and self-produced reducing gas fed earlier and are heated to the temperature that needs in heat accumulating type or the continuous furnace before feeding reduction shaft furnace.The present invention adopts the fuel of low-heat value gas as heat accumulating type or continuous furnace, with the reduction tail gas that replaces being produced by reduction shaft furnace, reduction tail gas is all cemented out, and as self-produced reducing gas, with reasonable energy utilization, saves the energy after purifying treatment.The low-heat value gas that adopts mainly contains blast furnace gas, coal layer underground gasifying gas, coal mine mash gas, producer gas, melting and reducing tail gas etc.
Transition gas when startup source of the gas when the present invention utilizes one or more gas mixture in the nitrogen more than needed of steelworks or coke-oven gas, gas maked coal, Sweet natural gas, the coal-seam gas as the production blow-on and blowing out.During blow-on, to start source of the gas earlier is full of in the reduction shaft furnace, air is discharged, the startup source of the gas that will be heated to 900～1300 ℃ is again sent into reduction shaft furnace, make the part of coal generation pyrolysis in the iron ore briquet, the coal pyrolysis gas that produces mixes formation reduction tail gas and discharges outside the shaft furnace with the startup source of the gas, after purifying treatment, form and mix self-produced reducing gas, after self-produced reducing gas to be mixed satisfies circulation heat-carrying transfer heat, gradually reduce and start the source of the gas add-on, until closing the startup gas source valve fully, will all adopt self-produced reducing gas after the purification during boundary as reducing gas.
When blowing out, purge and replace the reducing gas in regenerator, pipeline and the reduction shaft furnace in the reduction flow process with starting source of the gas, and progressively cooling makes the stopping of reaction, stops to produce.Also can under the state of self-produced reducing gas, carry out the blowing out operation, but want strictness to follow operating instructions.
The present invention utilizes the self-produced reducing gas of iron ore briquet to produce direct-reduced iron, not only solved the demand of reducing gas by self, needn't provide reducing gas specially by the outside again, and can utilize low thermal mass coal gas such as blast furnace gas as thermal source, the step of having realized resource rationally utilizes, and has reduced energy consumption and production cost significantly.
Compare with blast furnace iron-making process, the present invention has remarkable advantages.The present invention is reduced to a directly reduction operation with ironmaking, coking, the sintering circuit of blast furnace ironmaking, and main equipment reduces, and counter investment reduces, energy consumption reduces significantly, pollute significantly and reduce, production cost reduces significantly, and the coal consumption of producing 1 ton of direct-reduced iron only is 218～345kg.
The present invention has made full use of the hydrogen in the coal, utilizes H
2The pyrolysis coal makes gasification, and reaction heat also all is utilized; Utilize coal hydrogenation liquefaction, make between coal grain and the coal grain and dissolve each other, coal grain and iron ore concentrate dissolve each other, softening, the liquefaction by coal, vaporize, curing, kept the intensity of iron ore briquet, realized the solid-state direct reduction of iron ore briquet.
The present invention all with the coal in the iron ore briquet as reductive agent, the gas that produces with the coal pyrolyzing is as reducing gas, with the fuel of low-heat value gas as the heating reducing gas, reduction of iron ore is produced direct-reduced iron, reduced the greenhouse gas emission that the low-heat value gas emptying causes on the one hand, on the other hand to CO, H in the reduction tail gas
2, CH
4, CO
2Isothermal chamber gas is recycled, and has realized the zero release of direct-reduced iron production process percent of greenhouse gases.
The present invention does not have solid waste discharge in process of production, and self-produced reducing gas is removing sulfide and CO
2After recycle, can realize cleaner production.
The present invention will reduce the CO that removes in the tail gas
2After the recovery, make compressed gas, liquefied gas or make dry ice, can be applied to foodstuffs industry and electric furnace connects steel, perhaps be used as the plant gas fertilizer of warmhouse booth.Thereby realize CO
2The ecological circulation utilization.
Embodiment
The material operation scheme: with the iron ore briquet from reduction shaft furnace top loading mouth is packed shaft furnace into, sealing gland enters the reduction chamber of shaft furnace on the process, pass through preheating section (＜200 ℃), pyrolysis of coal section (200～618 ℃), pyrolysis of coal and reduction coexistence section (618～900 ℃), reduction section (＞900 ℃) generation direct-reduced iron from top to bottom, direct-reduced iron is cooled to below 300 ℃ by cooling section, and process reduction sealing gland is down discharged shaft furnace by removal device.
Reducing gas operation scheme: be ready to N before the blow-on
2As starting source of the gas, with N
2Charge in the pipeline of coking chamber, reduction air chamber, reducing gas regenerative furnace, top gas refining plant, cooling recirculation system and connection thereof in the reduction shaft furnace, and equipment and ducted air are all ejected and clean totally.
By the reducing gas regenerative furnace with N
2Be heated to 900～1300 ℃, by pipe-line transportation in shaft furnace, arrive the shaft furnace top through reduction section, pyrolysis of coal and reduction coexistence section, pyrolysis of coal section and preheating section from bottom to top, temperature drops to 200～350 ℃, the reduction tail gas that generation is made up of reduction tail gas and coal pyrolysis gas is drawn shaft furnace through the shaft furnace top duct.
The reduction tail gas of drawing from the shaft furnace top is lowered the temperature, dedusting, is removed tar, takes off H by the top gas refining plant
2O, desulfurization, take off CO
2After the purification, become and contain H
2, CO, CH
4And N
2Self-produced reducing gas, send into the reducing gas regenerative furnace through air pump pressurization, through the reducing gas regenerative furnace self-produced reducing gas is heated to 900～1300 ℃, again by pipe-line transportation in shaft furnace, so realize the continuous circulation of self-produced reducing gas.
Reducing gas heating operation scheme.With the method for heating iron-smelting blast furnace combustion air, use the blast furnace (BF) gas heating reducing gas after purifying.Wherein, regenerative furnace burning blast furnace (BF) gas heating checker brick or refractory ball make it accumulation of heat, reach the processing requirement temperature after, remove to heat another regenerative furnace again; Normal temperature reducing gas after purifying is sent into first regenerative furnace with the air pump pressurization, absorb the heat of checker brick or refractory ball after, self-produced reducing gas temperature reaches 900～1300 ℃, through pipe-line transportation in shaft furnace.By 2～4 regenerative furnaces burn in turn accumulation of heat and the heating self-produced reducing gas.So continually, realize the circulation of self-produced reducing gas and top gas.
Cold gas operation scheme: the cold reducing gas of normal temperature is pressurizeed by air pump, send into the shaft furnace, draw shaft furnace, become high-temperature gas behind the absorption high temperature reduction iron heat from the cooling section upper end from the lower end of reduction shaft furnace cooling section.The high temperature reduction gas of drawing shaft furnace imports in the reducing gas after heat exchange is cooled to normal temperature, by the air pump pressurization, sends into the shaft furnace from the lower end of shaft furnace cooling section again.So constantly circulation realizes the cooling to direct-reduced iron.
Charging and bottom discharge sealing means on the shaft furnace: to be higher than the N of furnace inner gas pressure
2Secluding air.
Claims (8)
1. the self-produced reducing gas of the iron ore briquet method of producing direct-reduced iron, be under the high temperature reduction atmosphere, utilize coal in the iron ore briquet as reductive agent, with reduction of iron ore, to produce direct-reduced iron, the gas that it is characterized in that all using the generation of coal pyrolyzing is as reducing gas, and concrete grammar is:
To start source of the gas earlier and be full of reduction shaft furnace, and displace furnace air, the startup source of the gas that will be heated to 900～1300 ℃ again feeds in the reduction shaft furnace, and heating iron ore briquet makes in the pelletizing part of coal pyrolysis produce and contains H
2, CO and CH
4Pyrolysis gas, part of coal is as the reductive agent reducing iron ore, produces to contain CO
2And H
2The reduction tail gas of O;
The pyrolysis gas that produces is discharged by furnace roof with reduction tail gas, through desulfurization, take off CO
2After the purifying treatment, become self-produced reducing gas;
Self-produced reducing gas with heating progressively substitutes high startup temperature source of the gas, feeds in the reduction shaft furnace until replacing high startup temperature source of the gas fully, continues heating iron ore briquet, produces new pyrolysis gas and reduction tail gas, by the furnace roof discharge, through desulfurization, take off CO
2After the purifying treatment, become self-produced reducing gas, form the cyclic production and the use of self-produced reducing gas, simultaneously, self-produced reducing gas is also participated in the reduction reaction of iron ore in the part iron ore briquet directly, and produces reduction tail gas;
Circulation so repeatedly, the continuous production of realization direct-reduced iron.
2. the method for production direct-reduced iron according to claim 1 is characterized in that described startup source of the gas is one or more the mixed gas in nitrogen, coke(oven)gas, gas maked coal, Sweet natural gas, the coal-seam gas.
3. the method for production direct-reduced iron according to claim 1 is characterized in that mixing oxygen in self-produced reducing gas.
4. the method for production direct-reduced iron according to claim 3, the method that it is characterized in that mixing oxygen in self-produced reducing gas are that oxygen and the self-produced reducing gas burning of part are produced high-temperature gas, high-temperature gas are blended in the self-produced reducing gas again.
5. the method for production direct-reduced iron according to claim 3, the method that it is characterized in that mixing oxygen in self-produced reducing gas is to adopt the needle-like oxygen supply, and according to self-produced reducing gas: oxygen=10～100: 1 volume ratio is directly mixed oxygen in self-produced reducing gas.
6. the method for production direct-reduced iron according to claim 1 is characterized in that the pyrolysis gas and the reduction tail gas of being discharged by furnace roof removes tar, dust through cooling, desulfurization, removes H
2O, remove CO
2After the purifying treatment, become self-produced reducing gas.
7. the method for production direct-reduced iron according to claim 1 is characterized in that adopting heat accumulating type or continuous furnace, with low-heat value gas act as a fuel heating starting source of the gas and self-produced reducing gas.
8. the method for production direct-reduced iron according to claim 7 is characterized in that described low-heat value gas is blast furnace gas, coal layer underground gasifying gas, coal mine mash gas, producer gas or melting and reducing tail gas.
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| CN101787408B (en) * | 2010-03-12 | 2011-12-21 | 苏亚杰 | Method for producing direct reduced iron by utilizing sensible heat of raw gas |
| CN101871031B (en) * | 2010-06-01 | 2011-08-03 | 中国石油大学(北京) | Method and equipment for preparing reducing gas from coke oven gas to produce sponge iron |
| CN102888235B (en) * | 2012-09-20 | 2014-04-02 | 中国科学院过程工程研究所 | Device and method for performing pyrolysis on solid fuel and performing reductive coupling on iron ore |
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| CN109852424B (en) * | 2019-01-02 | 2021-04-27 | 新奥科技发展有限公司 | Coal gasification iron-making method and coal gasification iron-making gasification furnace |
| CN109868335B (en) * | 2019-03-19 | 2021-01-26 | 重庆大学 | System and method for closed-loop utilization of tail gas in iron ore reduction process |
| CN112813219B (en) * | 2021-02-05 | 2023-07-25 | 辽宁科技大学 | System and process for realizing near zero emission by directly reducing iron by ammonia gas |
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| US4678508A (en) * | 1984-09-12 | 1987-07-07 | Kabushiki Kaisha Kobe Seiko Sho | Method for fluidized bed reduction of iron ore |
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| US4678508A (en) * | 1984-09-12 | 1987-07-07 | Kabushiki Kaisha Kobe Seiko Sho | Method for fluidized bed reduction of iron ore |
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